Optically active phosphine derivative having at least two vinyl groups, polymer produced using the same as monomer, and transition metal complexes of these

ABSTRACT

A transition metal complex of a polymer of 2&#39;-diarylphosphino-1,1&#39;-biphenylen-2-yloxy(6,6&#39;-divinyl-1,1&#39;-binaphthalene-2,2&#39;-diyloxy)phosphine derivative is disclosed, which is represented by general formula (I): ##STR1## wherein Ar is an optionally substituted phenyl or naphthyl; R 1  and R 2  each independently is a hydrogen atom, a lower alkyl, a lower alkoxy, etc.; and R 3  is a lower alkyl, a lower alkoxy, etc.; provided that R 2  and R 3  may be bonded to each other to form a hydrocarbon ring, which may have one or more substituents selected from lower alkyl groups, halogen atoms, vinyl, etc. Also disclosed are a polymer having structural units derived from the phosphine derivative and a transition metal complex obtained by causing a transition metal compound to act on the phosphine derivative or the polymer. A novel polymer-supported ligand is provided which, when used as a catalyst for asymmetric syntheses, gives satisfactory results concerning catalytic activity, enantiomer excess, etc.

FIELD OF THE INVENTION

The present invention relates to a phosphine derivative, a polymerhaving structural units derived from the same as a polymer-forming basemonomer, and complexes of these with a transition metal such as rhodium.This invention further relates to a method for obtaining an opticallyactive compound in the presence of these transition metal complexes,which are utilizable as useful catalysts in asymmetric hydroformylationreactions.

BACKGROUND OF THE INVENTION

Many transition metal complexes have hitherto been used as catalysts fororganic synthesis reactions. In particular, noble-metal complexes areextensively utilized, despite their expensiveness, since they are stableand easy to handle. Many investigations were made on syntheses usingtransition metal complexes including such noble-metal complexes ascatalysts. As a result, many reports have been made on techniques makingit possible to carry out organic synthesis reactions, includingasymmetric reactions, which have been regarded as impossible with anyconventional technique.

There are various types of optically active ligands for use in suchasymmetric-synthesis catalysts. Among the ligands for use in asymmetrichydroformylation reactions using transition metal-phosphine complexes,one of the ligands having the highest degree of chiral recognition is2-diphenylphosphino-1,1'-binaphthalen-2'-yloxy(1,1'-binaphthalene-2,2'-diyloxy)phosphine(hereinafter referred to simply as "BINAPHOS"). There are reports on theuse of a rhodium complex containing BINAPHOS as a ligand in an olefinhydroformylation reaction, which is a reaction for forming asymmetriccarbon-carbon bonds (see JP-A-6-263776 and JP-A-6-316560). (The term"JP-A" as used herein means an "unexamined published Japanese patentapplication".)

However, such expensive catalysts are unable to be recovered, or can berecovered only by a complicated separation method which is alwaysaccompanied by an undesirable loss. Furthermore, reuse of the recoveredhomogeneous catalysts is impossible and/or uneconomical. There has hencebeen a desire for a catalyst which can be easily recovered and reusedand is capable of fully retaining its activity and, in particular,selectivity during repeated use.

With respect to synthetic chiral polymers, the application thereof toracemate separation media, reagents for asymmetric syntheses, catalysts,and the like is being extensively investigated. Rapid progress is beingmade recently in investigations on asymmetry recognition among thevarious functions of these chiral polymers. In particular, in theapplication thereof to stereoselective organic reactions, the chiralpolymers can be used in a method different from those for generalhomogenous reaction systems because a specific reaction fieldconstituted of the polymers is used.

Use of a polymeric reagent or polymeric catalyst in organic syntheseshas an advantage that industrial processes can be improved because thereaction products can be easily separated and the reagent or catalystcan be reused.

For example, a report has been made on a process comprising reacting anoptically active amino acid with 4-vinylbenzenesulfonyl chloride toobtain a chiral monomer, polymerizing the monomer with styrene anddivinylbenzene to obtain a chiral polymer, ##STR2## reacting thispolymeric ligand with diborane to obtain a polymer-supported chiraloxaborolidinone, and using this compound as a Lewis acid catalyst toconduct the Diels-Alder reaction of cyclopentadiene with methacrolein(see S. Itsuno et al., Tetrahedron: Asymmetry, 1995, Vol. 6, p. 2547).

There also is a report on a method in which a Mn(II)-salen complex ispolymerized ##STR3## and the resultant polymer is used to conduct theasymmetric epoxidation reaction of an olefin (see S. Sivaram et al.,Tetrahedron: Asymmetry, 1995, Vol. 6, p. 2105).

Furthermore, there is a report on a method which comprisescopolymerizing optically active2-p-styryl-4,5-bis[(dibenzophosphoryl)methyl]-1,3-dioxolane with styreneto obtain a chiral polymer, ##STR4## coordinating platinum chloride tothis polymeric ligand, and using the resultant coordination compound toconduct the hydroformylation reaction of styrene in the presence of tinchloride (see J. K. Stille et al., J. Org. Chem., 1986, Vol. 51, p.4189).

However, all the prior art techniques have insufficient catalyticactivity or result in an enantiomer excess lower than those in the caseof reacting monomers. Any of those prior art techniques has not been putto industrial use.

SUMMARY OF THE INVENTION

As described above, there has been a desire for a polymer-supportedligand which, when used as a catalyst for asymmetric synthesisreactions, gives satisfactory results concerning catalytic activity,enantiomer excess, etc. An object of the present invention is to meetthese requirements.

The present inventors have found that a polymeric ligand obtained bysynthesizing a monomer which comprises a biphenyl framework having adiarylphosphino group at the 2'-position and a phosphite at the2-position and in which the phosphite moiety has a naphthyl frameworkhaving two vinyl groups respectively at the 6- and 6'-positions, andthen copolymerizing the monomer with a styrene derivative and adivinylbenzene derivative is an excellent ligand for use in asymmetriccatalytic reactions. The present invention has been completed based onthis finding.

The present invention provides a2'-diarylphosphino-1,1'-biphenylen-2-yloxy(6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy)phosphinederivative represented by the following general formula (I): ##STR5##wherein Ar is an optionally substituted phenyl group or an optionallysubstituted naphthyl group; R¹ and R² each independently is a hydrogenatom, a lower alkyl group, a lower alkoxy group, a halogen atom, ahalogen-substituted lower alkyl group, or a benzyloxy group; and R³ is alower alkyl group, a lower alkoxy group, a halogen atom, ahalogen-substituted lower alkyl group, or a benzyloxy group; providedthat R² and R³ may be bonded to each other to form a hydrocarbon ring,which may have one or more substituents selected from lower alkylgroups, halogen atoms, lower alkoxy groups, halogenated lower alkylgroups, a benzyloxy group, and a vinyl group.

The present invention further provides an oligomer or polymer havingstructural units derived from a2'-diarylphosphino-1,1'-biphenylen-2-yloxy(6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy)phosphinederivative which are represented by the following general formula (III):##STR6## wherein R¹, R², R³, and Ar have the same meanings as definedabove; and k is an integer of 2 to 100.

The present invention furthermore provides transition metal complexesobtained by causing a transition metal compound to act on the compoundrepresented by general formula (I) and on the polymer represented bygeneral formula (III), respectively.

Another object of the present invention is to provide a process forproducing an optically active α-methylaldehyde compound represented bythe following general formula (B): ##STR7## wherein R⁵ is an alkyl grouphaving 1 to 8 carbon atoms, an optionally substituted phenyl group, anaphthyl group, or an acetoxy group,

which comprises subjecting an olefin compound represented by thefollowing general formula (A): ##STR8## wherein R⁵ has the same meaningas defined above, to asymmetric hydroformylation in the presence of anyof the transition metal complexes.

DETAILED DESCRIPTION OF THE INVENTION

In compound (I) of the present invention, Ar is an optionallysubstituted phenyl group or an optionally substituted naphthyl group.Examples of the substituents thereof include lower alkyl groups having 1to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl,t-butyl, and isobutyl, halogen atoms such as fluorine, chlorine, andbromine, lower alkoxy groups having 1 to 4 carbon atoms, such asmethoxy, ethoxy, propoxy, and butoxy, halogenated lower alkyl groupssuch as trifluoromethyl and trichloromethyl, and benzyloxy. Preferredexamples of Ar include phenyl, 4-tolyl, 4-methoxyphenyl, 3,5-xylyl, andnaphthyl.

Examples of R¹ and R² include a hydrogen atom, lower alkyl groups having1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl,t-butyl, and isobutyl, halogen atoms such as fluorine, chlorine, andbromine, lower alkoxy groups having 1 to 4 carbon atoms, such asmethoxy, ethoxy, propoxy, and butoxy, halogenated lower alkyl groupssuch as trifluoromethyl and trichloromethyl, and benzyloxy.

Examples of R³ include lower alkyl groups having 1 to 4 carbon atoms,such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, andisobutyl, halogen atoms such as fluorine, chlorine, and bromine, loweralkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy,propoxy, and butoxy, halogenated lower alkyl groups such astrifluoromethyl and trichloromethyl, and benzyloxy.

In the case where R² and R³ are bonded to each other to form ahydrocarbon ring, examples of the hydrocarbon ring include benzene andcyclohexane rings which each may have one or more substituents. Examplesof the substituents include lower alkyl groups having 1 to 4 carbonatoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, andisobutyl, halogen atoms such as fluorine, chlorine, and bromine, loweralkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy,propoxy, and butoxy, halogenated lower alkyl groups such astrifluoromethyl and trichloromethyl, benzyloxy, and vinyl.

Compound (I) of the present invention is produced, for example, by aprocess shown by the following reaction scheme, in which the targetcompound is represented by general formula (I) wherein Ar is phenyl, R¹is a hydrogen atom, and R² and R³ are bonded to each other to form ahydrocarbon ring which is a benzene ring. ##STR9##

An optically active binaphthol (VII) as a starting material is reactedby a method described in the literature (M. Vondenhof and J. Mattay,Tetrahedron Lett., 1990, Vol. 31, pp. 985-988; L. Kurz, G. Lee, D.Morgans, Jr., M. J. Waldyke, and T. Ward, Tetrahedron Lett., 1990, Vol.31, pp. 6321-6324) and by a method described in the literature (Y.Uozumi, A. Tanahashi, S.-Y. Lee, and T. Hayashi, J. Org. Chem., 1993,Vol. 58, pp. 1945-1948). That is, the binaphthol (VII) is reacted withtrifluoromethanesulfonic anhydride (Tf₂ O) using pyridine in methylenechloride to convert compound (VII) to2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthyl (VIII), which isreacted with diphenylphosphine oxide (Ph₂ PHO) in the presence of acatalytic amount of a palladium-phosphine complex, whereby2'-diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl (IX)is synthesized. Compound (IX) is reduced with trichlorosilane (HSiCl₃)to obtain2'-diphenylphosphino-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl (X),which is hydrolyzed with lithium hydroxide (LiOH) to obtain2'-diphenylphosphino-2-hydroxy-1,1'-binaphthyl (XI). ##STR10##

An optically active binaphthol (VII) is reacted with bromine in aceticanhydride to obtain 6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl (XII).The hydroxyl groups of compound (XII) are protected usingtert-butyldimethylsilyl oxytriflate (TBDMSOTf) and 2,6-lutidine toobtain 6,6'-dibromo-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl(XIII). Compound (XIII) is converted to an anion form usingsec-butyllithium (sec-BuLi), and dimethylformamide (DMF) is caused toact thereon to obtain6,6'-diformyl-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl(XIV). Compound (XIV) is reacted with triphenylmethylphosphonium bromide(Ph₃ P⁺ CH₃ Br⁻) and potassium t-butoxide (t-BuOK) to obtain6,6'-divinyl-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl (XV).Compound (XV) is reacted with tetrabutylammonium fluoride (TBAF) forsilyl removal to obtain 6,6'-divinyl-2,2'-dihydroxy-1,1'-binaphthyl,which is heated together with phosphorus trichloride to obtain6,6'-divinyl-1,1'-binaphthalene-2,2'-dioxychlorophosphine (XVI). The6,6'-divinyl-1,1'-binaphthalene-2,2'-dioxychlorophosphine (XVI) isreacted with 2'-diphenylphosphino-2-hydroxy-1,1'-binaphthyl (XI) in thepresence of triethylamine (NEt₃) to obtain2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy(6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy)phosphine(XVII).

The following is an example of processes for producing the compound (I)wherein Ar is phenyl, R¹ is a hydrogen atom, and R² and R³ form ahydrocarbon ring which is a benzene ring having a vinyl group at the6-position. ##STR11##

An optically active binaphthol (VII) as a starting material is reactedby a method described in the literature (M. Vondenhof and J. Mattay,Tetrahedron Lett., 1990, Vol. 31, pp. 985-988; L. Kurz, G. Lee, D.Morgans, Jr., M. J. Waldyke, and T. Ward, Tetrahedron Lett., 1990, Vol.31, pp. 6321-6324) and by a method described in the literature (Y.Uozumi, A. Tanahashi, S.-Y. Lee, and T. Hayashi, J. Org. Chem., 1993,Vol. 58, pp. 1945-1948). That is, the binaphthol (VII) is reacted withtrifluoromethanesulfonic anhydride (Tf₂ O) using pyridine in methylenechloride to convert compound (VII) to2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthyl (VIII), which isreacted with diphenylphosphine oxide (Ph₂ PHO) in the presence of acatalytic amount of a palladium-phosphine complex, whereby2'-diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl (IX)can be synthesized. Compound (IX) is hydrolyzed with lithium hydroxide(LiOH) to obtain 2'-diphenylphosphinyl-2-hydroxy-1,1'-binaphthyl(XVIII), which is brominated in dioxane to obtain2'-diphenylphosphinyl-2-hydroxy-6-bromo-1,1'-binaphthyl (XIX). Compound(XIX) is reduced with trichlorosilane (HSiCl₃) to obtain2'-diphenylphosphino-2-hydroxy-6-bromo-1,1'-binaphthyl (XX), which isreacted with 2-vinyl-5,5-dimethyl-1,3-dioxa-2-borinane using a palladiumcatalyst by a method described in the literature (Y. Miyaura and A.Suzuki, J. C. S. Chem. Commun., 1979, p. 866) to obtain2'-diphenylphosphino-2-hydroxy-6-vinyl-1,1'-binaphthyl (XXI).

Finally, the 2'-diphenylphosphino-2-hydroxy-6-vinyl-1,1'-binaphthyl(XXI) is reacted with the6,6'-divinyl-1,1'-binaphthalene-2,2'-dioxychlorophosphine (XVI) obtainedabove to thereby obtain2'-diphenylphosphino-6-vinyl-1,1'-binaphthalen-2-yloxy(6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy)phosphine(XXII) as the target compound.

The processes described above yield the compound represented by generalformula (I) wherein Ar is phenyl, R¹ is a hydrogen atom, and R² and R³form a hydrocarbon ring which is a benzene ring and the compoundrepresented by general formula (I) wherein Ar is phenyl, R¹ is ahydrogen atom, and R² and R³ form a hydrocarbon ring which is a benzenering having a vinyl group at the 6-position. However, these processescan be utilized also for obtaining other compounds represented bygeneral formula (I).

Compound (I) of the present invention, obtained by the method describedabove, functions as a ligand to form a complex with a transition metal.Examples of the metal as a component of the complex include rhodium,iridium, palladium, platinum, cobalt, and nickel. Examples of thecomplex are given below. In the following formulae showing transitionmetal complexes, "L" represents compound (I) of the present invention,"cod" 1,5-cyclooctadiene, "nbd" norbornadiene, "Ph" phenyl, "Ac" acetyl,"OAc" acetoxy, and "acac" acetylacetonato. "L" represents(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphineas a typical example of compound (I) of the present invention.

Rhodium Complexes:

Examples of rhodium compounds used as complex precursors for formingrhodium complexes include the following.

RhCl₃, RhBr₃, RhI₃, [Rh(cod)Cl]₂, [Rh(cod)Br]₂, [Rh(cod)I)]₂,[Rh(nbd)Cl]₂, [Rh(nbd)Br]₂, [Rh(nbd)I]₂, [Rh(cod)(OAc)]₂,[Rh(nbd)(OAc)]₂, Rh(cod)(acac), Rh(nbd)(acac), Rh(CO)₂ (acac), [Rh(CO)₂Cl]₂, [Rh(CO)₂ Br]₂, [Rh(CO)₂ I]₂, [Rh(cod)₂ ]BF₄, [Rh(cod)₂ ]ClO₄,[Rh(cod)₂ ]PF₆, [Rh(cod)₂ ]BPh₄, [Rh(nbd)₂ ]BF₄, [Rh(nbd)₂ ]ClO₄,[Rh(nbd)₂ ]PF₆, [Rh(nbd)₂ ]BPh₄

Such rhodium complexes may be produced, for example, by reactingdicarbonylacetylacetonatorhodium (Rh(CO)₂ (acac)) with compound (I) ofthe present invention according to a method described in the literature(N. Sakai, S. Mano, K. Nozaki, H. Takaya, J. Am. Chem. Soc., 1993, Vol.115, p. 7033). Specific examples of the rhodium complexes obtainedinclude the following.

Rh(acac)(L)

Rh(cod)Cl(L)

Rh(nbd)Cl(L)

Rh(cod)Br(L)

Rh(nbd)Br(L)

Rh(cod)(L)

Rh(nbd)(L)

Rh(OAc)(L)

RhH(CO)(L)

[Rh(cod)(L)]ClO₄

[Rh(cod)(L)]BF₄

[Rh(cod)(L)]PF₆

[Rh(nbd)(L)]ClO₄

[Rh(nbd)(L)]BF₄

[Rh(nbd)(L)]PF₆

Palladium Complexes:

Examples of palladium compounds used as complex precursors for formingpalladium complexes include the following.

PdCl₃, PdBr₃, PdI₃, [(π-allyl)PdCl]₂, [(π-allyl)PdBr]₂, [(π-allyl)PdI]₂,[(π-mathallyl)PdCl]₂, [(π-methallyl)PdBr]₂, [(π-methallyl)PdI]₂, PdCl₂(CH₃ CN)₂, PdBr₂ (CH₃ CN)₂, PdI₂ (CH₃ CN)₂, PdCl₂ (C₆ H₅ CN)₂, PdBr₂ (C₆H₅ CN)₂, PdI₂ (C₆ H₅ CN)₂, PdCl₂ (cod), PdBr₂ (cod), PdI₂ (cod), PdCl₂(nbd), PdBr₂ (nbd), PdI₂ (nbd), Pd(OAc)₂, Pd(acac)₂

Such palladium complexes can be prepared by reacting L withπ-allylpalladium chloride ([(π-allyl)PdCl]₂) by a method described inthe literature (Y. Uozumi and T. Hayashi, J. Am. Chem. Soc., 1991, Vol.113, p. 9887). Specific examples of the palladium complexes include thefollowing.

PdCl₂ (L)

(π-allyl)Pd(L)

[Pd(L)]ClO₄

[Pd(L)]PF₆

[Pd(L)]BF₄

Platinum Complexes:

Examples of platinum compounds used as complex precursors for formingplatinum complexes include the following.

PtCl₃, PtBr₃, PtI₃, PtCl₂ (cod), PtBr₂ (cod), PtI₂ (cod), PtCl₂ (nbd),PtBr₂ (nbd), PtI₂ (nbd), Pt(acac)₂, K₂ PtCl₄, PtCl₂ (CH₃ CN)₂, PtBr₂(CH₃ CN)₂, PtI₂ (CH₃ CN)₂, PtCl₂ (PhCN)₂, PtBr₂ (PhCN)₂, PtI₂ (PhCN)₂

Such platinum complexes can be prepared by mixingdibenzonitriledichloroplatinum (PtCl₂ (PhCN)₂) with compound (I) inbenzene with heating according to a method described in the literature(G. Consiglio, S. S. A. Nefkens, A. Borer, Organometallics, 1991, Vol.10, p. 2046). A Lewis acid (e.g., SnCl₂) may be added if desired.Specific examples of the platinum complexes include the following.

PtCl₂ (L)

PtCl₂ (SnCl₂)(L)

PtCl(SnCl₃)(L)

Iridium Complexes:

Examples of iridium compounds used as complex precursors for formingiridium complexes include the following.

IrCl₃, IrBr₃, IrI₃, [Ir(cod)Cl]₂, [Ir(cod)Br]₂, [Ir(cod)I]₂,[Ir(nbd)Cl]₂, [Ir(nbd)Br]₂, [Ir(nbd)I]₂, [Ir(cod)(OAc)]₂,[Ir(nbd)(OAc)]₂, Ir(cod)(acac), Ir(nbd)(acac), Ir(CO)₂ (acac), [Ir(CO)₂Cl]₂, [Ir(CO)₂ Br]₂, [Ir(CO)₂ I]₂, [Ir(cod)₂ ]BF₄, [Ir(cod)₂ ]ClO₄,[Ir(cod)₂ ]PF₆, [Ir(cod)₂ ]BPh₄, [Ir(nbd)₂ ]BF₄, [Ir(nbd)₂ ]ClO₄,[Ir(nbd)₂ ]PF₆, [Ir(nbd)₂ ]BPh₄

Such iridium complexes can be prepared by mixing L with[(1,5-cyclooctadiene)(acetonitrile)iridium] tetrafluoroborate([Ir(cod)(CH₃ CN)₂ ]BF₄) in tetrahydrofuran according to a methoddescribed in the literature (K. Mashima, T. Akutagawa, X. Zhang, T.Taketomi, H. Kumobayashi, S. Akutagawa, J. Organomet. Chem., 1992, Vol.428, p. 213). Specific examples of the iridium complexes include thefollowing.

[Ir(cod)(L)]ClO₄

[Ir(cod)(L)]PF₆

[Ir(cod)(L)]BF₄

[Ir(nbd)(L)]ClO₄

[Ir(nbd)(L)]PF₆

[Ir(nbd)(L)]BF₄

Ir(cod)(L)Cl

Ir(nbd)(L)Cl

Ir(cod)(L)Br

Ir(nbd)(L)Br

Ir(cod)(L)

Ir(nbd)(L)

Ir(OAc)(L)

The present invention furthermore provides an oligomer or polymerproduced by polymerizing compound (I) of the present invention. Theoligomer or polymer has structural units derived from a2'-diarylphosphino-1,1'-biphenylen-2-yloxy(6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy)phosphinederivative which are represented by the following general formula (III):##STR12## wherein R¹, R², R³, and Ar have the same meanings as definedabove; and k is an integer of 2 to 100.

The polymer especially preferably has structural units derived fromcompounds which units are represented by the following general formulae(III), (IV), and (V): ##STR13## wherein R¹, R², R³, and Ar have the samemeanings as defined above; R⁴ is a hydrogen atom, a lower alkyl group, alower alkoxy group, or a halogen atom; R⁶ is a hydrogen atom or a methylgroup; k is an integer of 2 to 100; and l and m each is an integer of 0to 1,000; provided that (k+l+m) is from 10 to 1,000.

The polymer is preferably formed from monomers comprising compound (III)and at least one member selected from the group consisting of thestyrene derivative (IV) and the divinylbenzene derivative (V).

Examples of R⁴ in the styrene derivative monomer (IV) according to thepresent invention include a hydrogen atom, lower alkyl groups having 1to 4 carbon atoms, such as methyl, ethyl, isopropyl, n-butyl, andt-butyl, lower alkoxy groups having 1 to 4 carbon atoms, such asmethoxy, ethoxy, propoxy, and butoxy, and halogen atoms such as chlorineand bromine.

The polymer (III) of the present invention can be produced using a knownpolymerization method, e.g., solution polymerization or suspensionpolymerization.

This polymerization reaction is conducted as follows. The phosphinederivative (I) and the styrene derivative and/or divinylbenzenederivative are suspended or dissolved in an aqueous poly(vinyl alcohol)solution, a halogenated hydrocarbon, e.g., chloroform, or a hydrocarbon,e.g., toluene, and the resultant suspension or solution is introducedinto a reactor in an inert gas atmosphere, e.g., nitrogen or argon. Anazo compound, e.g., 2,2'-azobis(2,4-dimethylvaleronitrile) orazobisisobutyronitrile, or a peroxide is added thereto as a free-radicalinitiator, and the reaction mixture is reacted at ordinary pressure anda temperature of 60 to 100° C. for 1 hour to 2 days to thereby conductthe polymerization.

In producing the polymer of the present invention, the proportions ofcompounds (III), (IV), and (V) mixed together are represented by theratio between k, l, and m, i.e., molar ratio. Specifically, k:l:m is (2to 100):(0 to 1,000):(0 to 1,000). Preferably, k:l:m is (1 to 100):(100to 1,000):(0 to 1,000).

In the polymer of the present invention, the degrees of polymerizationof compounds (III), (IV), and (V) are shown by k, l, and m,respectively, and (k+l+m) is in the range of from 10 to 1,000.

The polymer (III) of the present invention thus obtained functions as aligand to form a complex with a transition metal. Examples of the metalas a component of the complex include rhodium, iridium, palladium,platinum, cobalt, and nickel. Examples of the complex are given below.In the following formulae showing transition metal complexes, "L"represents the monomer of compound (III) of the present invention, "cod"1,5-cyclooctadiene, "nbd" norbornadiene, "Ph" phenyl, "Ac" acetyl, "OAc"acetoxy, and "acac" acetylacetonato. "L" represents(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphinemonomer as a typical example of compound (III) of the present invention.Furthermore, "k" is an integer of 2 to 100.

Rhodium Complexes:

Examples of rhodium compounds used as complex precursors for formingrhodium complexes include the following.

RhCl₃, RhBr₃, RhI₃, [Rh(cod)Cl]₂, [Rh(cod)Br]₂, [Rh(cod)I]₂,[Rh(nbd)Cl]₂, [Rh(nbd)Br]₂, [Rh(nbd)I]₂, [Rh(cod)(OAc)]₂,[Rh(nbd)(OAc)]₂, Rh(cod)(acac), Rh(nbd)(acac), Rh(CO)₂ (acac), [Rh(CO)₂Cl]₂, [Rh(CO)₂ Br]₂, [Rh(CO)₂ I]₂, [Rh(cod)₂ ]BF₄, [Rh(cod)₂ ]ClO₄,[Rh(cod)₂ ]PF₆, [Rh(cod)₂ ]BPh₄, [Rh(nbd)₂ ]BF₄, [Rh(nbd)₂ ]ClO₄,[Rh(nbd)₂ ]PF₆, [Rh(nbd)₂ ]BPh₄

Such rhodium complexes may be produced, for example, by reactingdicarbonylacetylacetonatorhodium (Rh(CO)₂ (acac)) with compound (III) ofthe present invention according to a method described in the literature(N. Sakai, S. Mano, K. Nozaki, H. Takaya, J. Am. Chem. Soc., 1993, Vol.115, p. 7033). Specific examples of the rhodium complexes obtainedinclude the following.

[Rh(acac)]_(k) (L)

[Rh(cod)Cl]_(k) (L)

[Rh(nbd)Cl]_(k) (L)

[Rh(cod)Br]_(k) (L)

[Rh(nbd)Br]_(k) (L)

[Rh(cod)]_(k) (L)

[Rh(nbd)]_(k) (L)

[Rh(OAc)]_(k) (L)

[RhH(CO)₂ ]_(k) (L)

[Rh_(k) (cod)_(k) (L)](ClO₄)_(k)

[Rh_(k) (cod)_(k) (L)](BF₄)_(k)

[Rh_(k) (cod)_(k) (L)](PF₆)_(k)

[Rh_(k) (nbd)_(k) (L)](ClO₄)_(k)

[Rh_(k) (nbd)_(k) (L)](BF₄)_(k)

[Rh_(k) (nbd)_(k) (L)](PF₆)_(k)

Palladium Complexes:

Examples of palladium compounds used as complex precursors for formingpalladium complexes include the following.

PdCl₃, PdBr₃, PdI₃, [(π-allyl)PdCl]₂, [(π-allyl)PdBr]₂, [(π-allyl)PdI]₂,[(π-mathallyl)PdCl]₂, [(π-methallyl)PdBr]₂, [(π-methallyl)PdI]₂, PdCl₂(CH₃ CN)₂, PdBr₂ (CH₃ CN)₂, PdI₂ (CH₃ CN)₂, PdCl₂ (C₆ H₅ CN)₂, PdBr₂ (C₆H₅ CN)₂, PdI₂ (C₆ H₅ CN)₂, PdCl₂ (cod), PdBr₂ (cod), PdI₂ (cod), PdCl₂(nbd), PdBr₂ (nbd), PdI₂ (nbd), Pd(OAc)₂, Pd(acac)₂

Such palladium complexes can be prepared by reacting L withπ-allylpalladium chloride ([(π-allyl)PdCl]₂) by a method described inthe literature (Y. Uozumi and T. Hayashi, J. Am. Chem. Soc., 1991, Vol.113, p. 9887). Specific examples of the palladium complexes include thefollowing.

(PdCl₂)_(k) (L)

[(π-allyl)Pd]_(k) (L)

[Pd_(k) (L)](ClO₄)_(k)

[Pd_(k) (L)](PF₆)_(k)

[Pd_(k) (L)](BF₄)_(k)

Platinum Complexes:

Examples of platinum compounds used as complex precursors for formingplatinum complexes include the following.

PtCl₃, PtBr₃, PtI₃, PtCl₂ (cod), PtBr₂ (cod), PtI₂ (cod), PtCl₂ (nbd),PtBr₂ (nbd), PtI₂ (nbd), Pt(acac)₂, K₂ PtCl₄, PtCl₂ (CH₃ CN)₂, PtBr₂(CH₃ CN)₂, PtI₂ (CH₃ CN)₂, PtCl₂ (PhCN)₂, PtBr₂ (PhCN)₂, PtI₂ (PhCN)₂

Such platinum complexes can be prepared by mixingdibenzonitriledichloroplatinum (PtCl₂ (PhCN)₂) with compound (III) inbenzene with heating according to a method described in the literature(G. Consiglio, S. S. A. Nefkens, A. Borer, Organometallics, 1991, Vol.10, p. 2046). A Lewis acid (e.g., SnCl₂) may be added if desired.Specific examples of the platinum complexes include the following.

[PtCl₂ ]_(k) (L)

[PtCl₂ (SnCl₂)]_(k) (L)

[PtCl(SnCl₃)]_(k) (L)

Iridium Complexes:

Examples of iridium compounds used as complex precursors for formingiridium complexes include the following.

IrCl₃, IrBr₃, IrI₃, [Ir(cod)Cl]₂, [Ir(cod)Br]₂, [Ir(cod)I]₂,[Ir(nbd)Cl]₂, [Ir(nbd)Br]₂, [Ir(nbd)I]₂, [Ir(cod)(OAc)]₂,[Ir(nbd)(OAc)]₂, Ir(cod)(acac), Ir(nbd)(acac), Ir(CO)₂ (acac), [Ir(CO)₂Cl]₂, [Ir(CO)₂ Br]₂, [Ir(CO)₂ I]₂, [Ir(cod)₂ ]BF₄, [Ir(cod)₂ ]ClO₄,[Ir(cod)₂ ]PF₆, [Ir(cod)₂ ]BPh₄, [Ir(nbd)₂ ]BF₄, [Ir(nbd)₂ ]ClO₄,[Ir(nbd)₂ ]PF₆, [Ir(nbd)₂ ]BPh₄

Such iridium complexes can be prepared by mixing L with[(1,5-octadiene)(acetonitrile)iridium] tetrafluoroborate ([Ir(cod)(CH₃CN)₂ ]BF₄) in tetrahydrofuran according to a method described in theliterature (K. Mashima, T. Akutagawa, X. Zhang, T. Taketomi, H.Kumobayashi, S. Akutagawa, J. Organomet. Chem., 1992, Vol. 428, p. 213).Specific examples of the iridium complexes include the following.

[Ir_(k) (cod)_(k) (L)](ClO₄)_(k)

[Ir_(k) (cod)_(k) (L)](PF₆)_(k)

[Ir_(k) (cod)_(k) (L)](BF₄)_(k)

[Ir_(k) (nbd)_(k) (L)](ClO₄)_(k)

[Ir_(k) (nbd)_(k) (L)](PF₆)_(k)

[Ir_(k) (nbd)_(k) (L)](BF₄)_(k)

[Ir(cod)]_(k) (L)Cl_(k)

[Ir(nbd)]_(k) (L)Cl_(k)

[Ir(cod)]_(k) (L)Br_(k)

[Ir(nbd)]_(k) (L)Br_(k)

[Ir(cod)]_(k) (L)

[Ir(nbd)]_(k) (L)

[Ir(OAc)]_(k) (L)

The transition metal complex thus obtained from compound (I) of thepresent invention or the polymer comprising structural units (III) orcomprising structural units (III), (IV), and (V) and from a transitionmetal compound can be utilized as a catalyst for asymmetric syntheses.For example, the complex can be used as a catalyst for a process inwhich an olefin compound (A) shown below is reacted in a pressurizedatmosphere of carbon monoxide and hydrogen to produce an opticallyactive α-methylaldehyde compound (B) (hydroformylation reaction):##STR14## wherein R⁵ represents an alkyl group having 1 to 8 carbonatoms, an optionally substituted phenyl group, a naphthyl group, or anacetoxy group.

Namely, a transition metal complex containing as a ligand the phosphinederivative (I) or the oligomer or polymer (III) which each has beenselected with respect to (R),(S) isomer or (S),(R) isomer is used as acatalyst in the above reaction, whereby the optically active targetcompound having the desired absolute configuration can be synthesized.Examples of the group R⁵ in the olefin compound (A) used as a startingcompound in the above reaction include alkyl groups such as methyl,ethyl, propyl, isopropyl, n-butyl, t-butyl, pentyl, hexyl, heptyl, andoctyl, optionally substituted phenyl groups such as phenyl, 2-, 3-, or4-methoxyphenyl, 2-, 3-, or 4-chlorophenyl, 2-, 3-, or 4-fluorophenyl,2-, 3-, or 4-trifluoromethylphenyl, and 2-, 3-, or 4-tolyl, and othergroups including naphthyl, acetoxy, and phthaloyl.

On the other hand, a solvent such as, e.g., benzene, toluene, xylene,tetrahydrofuran, methylene chloride, 1,2-dichloroethane, or acetone canbe used for the reaction.

The amount of the catalyst used in the above reaction to the substrateis about from 0.01 to 10 mol %, preferably about from 0.05 to 5 mol %,in terms of the transition metal compound (II) or the transition metalcompound comprising structural units (VI) or comprising structural units(VI), (IV), and (V).

The reaction is usually carried out by maintaining the reaction mixtureat a temperature of about from 10 to 100° C., preferably about from 20to 50° C., for about from 10 minutes to 30 hours in an atmosphere ofcarbon monoxide and hydrogen having a pressure of about from 2 to 120atm. However, these conditions can be suitably changed according to theamounts of the reactants used, etc.

After the reaction, the polymeric transition metal compound of thepresent invention comprising structural units (VI) or structural units(VI), (IV), and (V) can be virtually completely separated from thereaction mixture by a simple method, e.g., centrifuging or filtration.The catalyst thus recovered can be reused.

The present invention will be explained below in more detail byreference to Examples, but the invention should not be construed asbeing limited thereby in any way.

The following apparatuses were used for property determination in theExamples.

¹ H NMR: JMN-EX-270 (270 MHz), manufactured by JEOL, Japan

³¹ p NMR: JMN-EX-270 (109 MHz), manufactured by JEOL

Angle of rotation: DIP-360, manufactured by JASCO Corp., Japan

GLC: GC-15A, manufactured by Shimadzu Corp., Japan

MASS: QP-1000, manufactured by Shimadzu Corp.

EXAMPLE 1 Synthesis of(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine(1) Synthesis of(R)-2,2'-bis[trifluoromethanesulfonyloxy]-1,1'-binaphthyl

In 181 ml of methylene chloride were dissolved 36.2 g (127 mmol) of(R)-binaphthol and 25.2 g (319 mmol) of pyridine. This solution wascooled to 0° C. Thereto was added dropwise 76.5 ml (271 mmol) oftrifluoromethanesulfonic anhydride. Thereafter, the resultant mixturewas stirred at room temperature for 18 hours, and 200 ml of 2 Nhydrochloric acid was then added to the reaction mixture to wash thesame. The organic layer was washed with water and a sodium chloridesolution, and the solvent was then distilled off, whereby 69.3 g of acrude reaction product was obtained. The crude product wasrecrystallized from 280 ml of hexane to obtain 64.1 g (yield, 92%) ofthe target compound.

¹ H NMR (CDCl₃) δ7.25-8.15 (m, aromatic)

(2) Synthesis of(R)-2'-diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl

In 100 ml of dimethyl sulfoxide (DMSO) were dissolved 11 g (20 mmol) of(R)-2,2'-bis[trifluoromethanesulfonyloxy]-1,1'-binaphthyl, 0.225 g (50mol %) of palladium acetate, and 0.43 g (50 mol %) of1,3-bis(diphenylphosphino)propane. This solution was stirred at roomtemperature for 1.5 hours. Thereto was added a solution prepared bydissolving 8.08 g (40 mmol) of diphenylphosphine oxide and 20 ml ofdiisopropylethylamine in 100 ml of dimethyl sulfoxide (DMSO). Theresultant mixture was stirred at 100° C. for 12 hours. After thereaction mixture was cooled to room temperature, 75 ml of methylenechloride was added thereto. This solution was cooled in an ice bath, and100 ml of 2 N hydrochloric acid was gradually added dropwise thereto.The resultant mixture was stirred at room temperature for 30 minutes andthen subjected to liquid separation. The aqueous layer was extractedwith methylene chloride. The resultant organic layer was collected,washed with water, and then dried with anhydrous magnesium sulfate. Thedried organic layer was concentrated for solvent removal, and theresidue was purified by silica gel column chromatography (hexane/ethylacetate=4/1 to 1/4 by volume). As a result, 11.5 g (yield, 96%) of thetarget compound was obtained as yellowish white crystals.

[α]_(D) ²⁴ 44.45° (c 0.50, CHCl₃)

¹ H NMR (CDCl₃) δ7.0-8.01 (m, aromatic)

³¹ P NMR (CDCl₃) δ28.73 (s)

(3) Synthesis of(R)-2'-diphenylphosphino-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl

In 22 ml of xylene was dissolved 400 mg (0.664 mmol) of(R)-2'-diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl.Thereto were added 1.20 g (12 mmol) of triethylamine and 1.62 g (12mmol) of trichlorosilane. The resultant mixture was stirred at 120° C.for 17 hours. After the reaction mixture was cooled to room temperature,4.4 ml of 35% sodium hydroxide solution was carefully added thereto.This mixture was stirred for further two hours and then subjected toliquid separation. The organic layer was washed twice with 30 ml ofsaturated sodium chloride solution and then dried with anhydrousmagnesium sulfate. The solvent was distilled off at a reduced pressureto thereby obtain the target compound as a crude reaction product. Thisunpurified compound as such was subjected to the following reaction.

(4) Synthesis of (R)-2'-diphenylphosphino-2-hydroxy-1,1'-binaphthyl

The(R)-2'-diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1'-binaphthylobtained above was dissolved in 7 ml of tetrahydrofuran. Thereto wereadded 335 mg (8.0 mmol) of lithium hydroxide monohydrate (LiOH.H₂ O) andpurified water (2.4 ml). After this mixture was stirred for 15 hours,the tetrahydrofuran was distilled off at a reduced pressure. To theresidue were added ether (10 ml) and 5% hydrochloric acid (10 ml). Theresultant mixture was stirred and then subjected to liquid separation.Thereafter, the organic layer was washed with water twice and then driedwith anhydrous magnesium sulfate. The dried organic layer wasconcentrated to distill off the solvent, and the residue was purified bysilica gel column chromatography (hexane/ethyl acetate=5/1 by volume).As a result, 153 mg of the target compound was obtained (yield based on(R)-2'-diphenylphosphinyl-2-trifluoromethanesulfonyloxy-1,1'-binaphthyl,51%).

(5) Synthesis of (S)-6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl

In 200 ml of glacial acetic acid was dissolved 28.63 g (0.1 mol) of(S)-binaphthol. After this solution was heated to 60° C., 32 g (0.2 mol)of bromine and 50 ml of glacial acetic acid were added thereto dropwise.The resultant mixture was stirred at that temperature for 30 minutes andthen at room temperature overnight. The solvent was distilled off at areduced pressure. As a result, 44.61 g of the target compound wasobtained.

(6) Synthesis of(S)-6,6'-dibromo-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl

In 20 ml of methylene chloride were dissolved 2.42 g (4.86 mmol) of(S)-6,6'-dibromo-2,2'-dihydroxy-1,1'-binaphthyl, 2.4 ml (10.5 mmol) oftert-butyldimethylsilyl triflate, and 1.2 ml (10.3 mmol) of2,6-lutidine. This solution was stirred at room temperature for 7 hours.Saturated aqueous sodium bicarbonate solution was added thereto, and theresultant mixture was subjected to liquid separation. Thereafter, theorganic layer was washed with saturated sodium chloride solution andwater and then dried with anhydrous magnesium sulfate. The solvent wasdistilled off at a reduced pressure, and the residue was purified bysilica gel column chromatography (hexane/ethyl acetate=5/1 by volume).As a result, 3.19 g (yield, 91%) of the target compound was obtained.

¹ H NMR (CDCl₃) δ-0.16 (s, 6H), 0.02 (s, 6H), 0.48 (s, 18H), 7.02 (d,J=8.91 Hz, 2H), 7.18 (d, J=8.91 Hz, 2H), 7.27 (dd, J=1.98, 8.91 Hz, 2H),7.72 (d, J=8.91 Hz, 2H), 7.97 (d, J=1.98 Hz, 2H)

(7) Synthesis of(S)-6,6'-diformyl-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl

Into an 80-ml Schlenk tube was introduced 2.19 g (3.26 mmol) of(S)-6,6'-dibromo-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl,followed by 12 ml of ether. Thereto was added dropwise sec-butyllithium(7.76 mmol, hexane solution). The resultant mixture was stirred at 0° C.for 2 hours. To this solution maintained at that temperature were added0.6 ml (7.76 mmol) of dimethylformamide and 5 ml of ether. After theresultant mixture was stirred for 12 hours, 3 N HCl was added thereto toterminate the reaction. The reaction mixture was neutralized withsaturated aqueous sodium bicarbonate solution and then subjected toliquid separation. The organic layer was washed with saturated sodiumchloride solution and then dried with anhydrous magnesium sulfate. Thedried organic layer was concentrated for solvent removal, and theresidue was purified by silica gel column chromatography (hexane/ethylacetate=4/1 by volume). As a result, 1.34 g (yield, 74%) of the targetcompound was obtained.

¹ H NMR (CDCl₃) δ-0.08 (s, 6H), 0.06 (s, 6H), 0.43 (s, 18H), 7.25-7.30(m, 2H), 7.69 (dd, J=1.65, 8.91 Hz, 2H), 8.02 (d, J=8.91 Hz, 2H), 8.34(d, J=1.65 Hz, 2H), 10.10 (s, 2H)

(8) Synthesis of(S)-6,6'-divinyl-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl

In 60 ml of ether were dissolved 3.05 g (5.34 mmol) of(S)-6,6'-diformyl-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyland 5.73 g (16.0 mmol) of triphenylmethylphosphonium bromide. Theretowas added 1.80 g (16.0 mmol) of potassium t-butoxide. This mixture wasstirred at room temperature for 4 hours. Water was added to the reactionmixture, and the resultant mixture was subjected to liquid separation.The organic layer was washed with saturated sodium chloride solution andwater and then dried with anhydrous magnesium sulfate. The dried organiclayer was concentrated for solvent removal, and the residue was purifiedby silica gel column chromatography (hexane/ethyl acetate=6/1 byvolume). As a result, 2.87 g (yield, 95%) of the target compound wasobtained.

¹ H NMR (CDCl₃) δ-0.21 (s, 6H), 0.02 (s, 6H), 0.50 (s, 18H), 5.23 (dd,J=0.99, 10.89 Hz, 2H), 5.75 (dd, J=0.99, 17.48 Hz, 2H), 6.83 (dd,J=10.89 17.48 Hz, 2H), 7.12-7.18 (m, 4H), 7.36 (dd, J=1.65, 8.91 Hz,2H), 7.73 (d, J=1.28 Hz, 2H), 7.78 (d, J=8.91 Hz, 2H)

(9) Synthesis of (S)-6,6'-divinyl-2,2'-dihydroxy-1,1'-binaphthyl

In 50 ml of tetrahydrofuran was dissolved 2.87 g (5.06 mmol) of(S)-6,6'-diformyl-2,2'-bis(tert-butyldimethylsilyloxy)-1,1'-binaphthyl.Thereto was added 5 ml of water, followed by a tetrahydrofuran solutionof tetramethylammonium fluoride (5.1 mmol). This mixture was stirred atroom temperature for 4 hours and then extracted with ether. The organiclayer obtained was dried with anhydrous magnesium sulfate. The driedorganic layer was concentrated for solvent removal, and the residue waspurified by silica gel column chromatography (hexane/ethyl acetate=1/1by volume). As a result, 0.77 g (yield, 45%) of the target compound wasobtained.

¹ H NMR (CDCl₃) δ5.01 (s, 2H), 5.28 (d, J=10.89 Hz, 2H), 5.78 (d,J=17.48 Hz, 2H), 6.84 (dd, J=10.89, 17.48 Hz, 2H), 7.11 (d, J=8.91 2H),7.37 (d, J=8.91 Hz, 2H), 7.46 (dd, J=1.65, 8.91 Hz, 2H), 7.82 (d, J=1.32Hz, 2H), 7.96 (d, J=8.91 Hz, 2H)

(10) Synthesis of(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine

In 6 ml of ether were dissolved 0.11 g (0.24 mmol) of(R)-2'-diphenylphosphino-2-hydroxy-1,1'-binaphthyl and 0.16 g (0.35mmol) of (S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-dioxychlorophosphine.Thereto were added dropwise at 0° C. 0.06 ml (0.43 mmol) oftriethylamine solution and 2 ml of ether. This mixture was stirred atthat temperature for 1 hour and then at room temperature for 24 hours.Ice water was added to the reaction mixture, and the resultant mixturewas subjected to liquid separation. Thereafter, the aqueous layer wasextracted with ether, and the resultant organic layer was dried withanhydrous magnesium sulfate. The dried organic layer was concentratedfor solvent removal, and the residue was purified by silica gel columnchromatography (hexane/methylene chloride=2/1 to 1/1 by volume). As aresult, 0.13 g (yield, 68%) of the target compound was obtained.

¹ H NMR (CDCl₃) δ5.30 (m, 2H), 5.80 (m, 2H), 6.02 (d, J=8.90 Hz, 1H),6.70-8.05 (m, 33H)

³¹ P NMR (CDCl₃) δ145.1 (d, J=30.5 Hz), -13.3 (d, J=30.5)

EXAMPLE 2 Synthesis of(R)-2'-diphenylphosphino-6-vinyl-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine(1) Synthesis of(R)-2,2'-bis[trifluoromethanesulfonyloxy]-1,1'-binaphthyl

In 181 ml of methylene chloride were dissolved 36.2 g (127 mmol) of(R)-binaphthol and 25.2 g (319 mmol) of pyridine. This solution wascooled to 0° C. Thereto was added dropwise 76.5 ml (271 mmol) of ananhydrous triflate. Thereafter, the resultant mixture was stirred atroom temperature for 18 hours, and 200 ml of 2 N hydrochloric acid wasthen added to the reaction mixture to wash the same. The organic layerwas washed with water and a sodium chloride solution, and the solventwas then distilled off, whereby 69.3 g of a crude reaction product wasobtained. The crude product was recrystallized from 280 ml of hexane toobtain 64.1 g (yield, 92%) of the target compound.

¹ H NMR (CDCl₃) δ7.25-8.15 (m, aromatic)

(2) Synthesis of(R)-2'-diphenylphosphinyl-2-[trifluoromethanesulfonyloxy]-1,1'-binaphthyl

In 100 ml of dimethyl sulfoxide were dissolved 11 g (20 mmol) of(R)-2,2'-bis[trifluoromethanesulfonyloxy]-1,1'-binaphthyl, 0.225 g (50mol %) of palladium acetate, and 0.43 g (50 mol %) of1,3-bis(diphenylphosphino)propane. This solution was stirred at roomtemperature for 1.5 hours. Thereto was added a solution prepared bydissolving 8.08 g (40 mmol) of diphenylphosphine oxide and 20 ml ofdiisopropylethylamine in 100 ml of dimethyl sulfoxide. The resultantmixture was stirred at 100° C. for 12 hours. After the reaction mixturewas cooled to room temperature, 75 ml of methylene chloride was addedthereto. This solution was cooled in an ice bath, and 100 ml of 2 Nhydrochloric acid was gradually added dropwise thereto. The resultantmixture was stirred at room temperature for 30 minutes and thensubjected to liquid separation. The aqueous layer was extracted withmethylene chloride. The resultant organic layer was collected, washedwith water, and then dried with magnesium sulfate. The dried organiclayer was concentrated for solvent removal, and the residue was purifiedby silica gel column chromatography (hexane/ethyl acetate=4/1 to 1/4 byvolume). As a result , 11.5 g (yield, 96%) of the target compound wasobtained as yellowish white crystals.

[α]_(D) ²⁴ 44.45° (c 0.50, CHCl₃)

¹ H NMR (CDCl₃) δ7.0-8.01 (m, aromatic)

³¹ P NMR (CDCl₃) δ28.73 (s)

(3) Synthesis of (R)-2'-diphenylphosphinyl-2-hydroxy-1,1'-binaphthyl

To 11.5 g (19.2 mmol) of(R)-2'-diphenylphosphinyl-2-[trifluoromethanesulfonyloxy]-1,1'-binaphthylwere added 2.42 g (57.6 mmol) of lithium hydroxide monohydrate,tetrahydrofuran (75 ml), and purified water (25 ml). This mixture wasstirred overnight. The tetrahydrofuran was distilled off at a reducedpressure, and toluene (30 ml) and 2 N hydrochloric acid (50 ml) wereadded. After the resultant mixture was stirred and then subjected toliquid separation, the organic layer was dried with anhydrous magnesiumsulfate. The solvent was then distilled off to obtain 9.03 g (yield,100%) of the target compound.

(4) Synthesis of(R)-6-bromo-2'-diphenylphosphinyl-2-hydroxy-1,1'-binaphthyl

In 150 ml of dioxane was dissolved 4 g (8.49 mmol) of(R)-2'-diphenylphosphinyl-2-hydroxy-1,1'-binaphthyl. Thereto was addeddropwise at 5° C. a solution of 1.75 ml (34 mmol) of bromine in 20 ml ofdioxane. After this mixture was stirred at room temperature for 2 hours,it was neutralized with an aqueous sodium thiosulfate solution and thenextracted with chloroform. The resultant organic layer was washed withsaturated sodium chloride solution and then dried with anhydrousmagnesium sulfate. The solvent was distilled off at a reduced pressureto obtain a yellow solid, which was purified by silica gel columnchromatography (methylene chloride/ethyl acetate=1/1 by volume). As aresult, 4.06 g (yield, 87%) of the target compound was obtained.

¹ H NMR (CDCl₃) δ9.05 (bs, 1H), 7.95-7.17 (m, 2H), 7.65-7.53 (m, 7H),7.42-7.32 (m, 2H), 7.26-7.17 (m, 2H), 7.06-6.88 (m, 3H), 6.81-6.72 (m,2H), 6.27 (d, J=8.91, 1H)

³¹ P NMR (CDCl₃) δ31.26 (s)

(5) Synthesis of(R)-6-bromo-2'-diphenylphosphino-2-hydroxy-1,1'-binaphthyl

In 40 ml of xylene was dissolved 3.09 g (5.63 mmol) of(R)-6-bromo-2'-diphenylphosphinyl-2-hydroxy-1,1'-binaphthyl. Thereto wasadded 15.7 ml (112 mmol) of triethylamine, followed by 5.7 ml (56.4mmol) of trichlorosilane. The resultant mixture was stirred at 110° C.for 22 hours. Saturated aqueous sodium bicarbonate solution was addedthereto to terminate the reaction. Thereafter, the reaction mixture wasfiltered to remove the salt, washed with toluene, and then subjected toliquid separation. The organic layer was dried with anhydrous magnesiumsulfate, and the solvent was distilled off. The residue was purified bysilica gel column chromatography (chloroform). As a result, 1.94 g(yield, 65%) of the target compound was obtained.

¹ H NMR (CDCl₃) δ7.96-7.80 (m, 4H), 7.52-7.43 (m, 2H), 7.33-6.98 (m,14H), 6.55 (d, J=8.91, 1H), 4.62 (s, 1H)

³¹ P NMR (CDCl₃) δ-12.82 (s)

(6) Synthesis of(R)-2'-diphenylphosphino-2-hydroxy-6-vinyl-1,1'-binaphthyl

In 12 ml of dimethylformamide were dissolved 1.0 g (1.88 mmol) of(R)-6-bromo-2'-diphenylphosphino-2-hydroxy-1,1'-binaphthyl, 210 mg(0.182 mmol) of Pd(PPh₃)₄, 0.4 ml (2.87 mmol) of2-vinyl-5,5-dimethyl-1,2-dioxa-3-borinane, and 0.965 g (4.54 mmol) oftripotassium phosphate monohydrate. This solution was stirred at 80° C.for 16 hours. The reaction mixture was diluted with water and thenextracted with diethyl ether. The resultant organic layer was washedwith saturated sodium chloride solution and then dried with anhydrousmagnesium sulfate. The solvent was distilled off, and the residue waspurified by silica gel column chromatography (chloroform). As a result,618 mg (yield, 68%) of the target compound was obtained.

¹ H NMR (CDCl₃) δ7.95-7.86 (m, 3H), 7.72 (bs, 1H), 7.54-7.01 (m, 1H),6.79 (dd, J=17.15, 10.55, 1H), 6.69 (d, J=8.91 Hz, 1H), 5.7 (d, J=17.15,1H), 5.22 (d, J=10.55, 1H), 4.53 (s, 1H)

³¹ P NMR (CDCl₃) δ-13.01 (s)

(7) Synthesis of(R)-2'-diphenylphosphino-6-vinyl-1,1-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine

In 20 ml of ether were dissolved 0.45 g (0.936 mmol) of(R)-2'-diphenylphosphino-2-hydroxy-6-vinyl-1,1'-binaphthyl and(S)-6,6'-divinyl-1,1'-binaphthylene-2,2'-dioxychlorophosphine (1.03mmol). The solution was cooled to 0° C., and 0.2 ml (1.44 mmol) oftriethylamine was added thereto. This mixture was stirred at roomtemperature for 24 hours. Ice water was then added thereto to terminatethe reaction, and the resultant mixture was subjected to liquidseparation. Thereafter, the aqueous layer was extracted with ether, andthe resultant organic layer was dried with magnesium sulfate. Thesolvent was distilled off, and the residue was purified by silica gelcolumn chromatography (hexane/methylene chloride=1/1 by volume). As aresult, 302 mg (yield, 38%) of the target compound was obtained.

¹ H NMR (CDCl₃) δ8.06-6.60 (m, 33H), 6.00 (d, J=8.91 Hz, 1H), 5.84-5.23(m, 6H)

³¹ P NMR (CDCl₃) δ146.0 (d, J=30.5 Hz), -13.2 (d, J=30.5 Hz)

EXAMPLE 3

(1) Suspension Copolymerization

To 0.4% aqueous poly(vinyl alcohol) solution was added, with sufficientstirring at 80° C., a solution prepared by dissolving 100 mg (0.122mmol) of(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine,0.45 ml (3.93 mmol) of styrene, 0.035 ml (0.135 mmol) of divinylbenzene,and 20.2 mg (0.0813 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile)(hereinafter abbreviated as V-65) in 0.75 ml of toluene. The reactionmixture was stirred for 24 hours at a rotational speed of 400 rpm. Thepolymerization product obtained was taken out by filtration, washed withwater and methanol, and then dried at a reduced pressure to obtain apolymer as a light-yellow solid.

(2) Solution Copolymerization in Chloroform

Into a 20-ml Schlenk tube were introduced 100 mg (0.122 mmol) of(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine,0.42 ml (3.66 mmol) of styrene, 0.11 ml (0.424 mmol) of divinylbenzene,20.1 mg (0.081 mmol) of V-65, and 1.5 ml of chloroform. The contentswere heated at 70° C. for 5 hours. Methanol was added to the reactionmixture which had solidified. As a result, a white precipitategenerated. The precipitate was taken out by filtration, washed withmethanol and toluene, and then dried at a reduced pressure to obtain apolymer as a light-yellow solid.

(3) Solution Copolymerization in Toluene

Into a 20-ml Schlenk tube were introduced 100 mg (0.122 mmol) of(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine,0.42 ml (3.66 mmol) of styrene, 0.11 ml (0.424 mmol) of divinylbenzene,20.1 mg (0.081 mmol) of V-65, and 1.5 ml of toluene. The contents wereheated at 70° C. for 5 hours. Methanol was added to the reaction mixturewhich had solidified. As a result, a white precipitate generated. Theprecipitate was taken out by filtration, washed with methanol andtoluene, and then dried at a reduced pressure to obtain a polymer as alight-yellow solid.

(4) Solution Copolymerization in Toluene

Into a 20-ml Schlenk tube were introduced 50 mg (0.061 mmol) of(R)-2'-diphenylphosphino-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine,0.27 ml (2.03 mmol) of divinylbenzene, 5.2 mg (0.021 mmol) of V-65, and0.5 ml of toluene. The contents were heated at 80° C. for 14 hours. MeOHwas added to the reaction mixture which had solidified, and theresultant precipitate was taken out by filtration, washed with MeOH, andthen dried at a reduced pressure to obtain a polymer as a light-yellowsolid.

EXAMPLE 4

Reaction of Polymer with Rhodium Dicarbonylacetylacetonate

Into a 20-ml Schlenk tube were introduced 4.1 mg (0.0159 mmol) ofRh(acac)(CO)₂, 304 mg of the polymer obtained in Example 3 (4)(containing 0.059 mmol in terms of monomer amount), and 5 ml of benzene.The contents were stirred with heating at room temperature for 2 hours.The reaction mixture was freeze-dried to obtain a reaction product as ayellowish orange solid.

EXAMPLE 5

Asymmetric Hydroformylation of Styrene

Into a 50-ml stainless-steel autoclave were introduced 61 mg of therhodium complex synthesized in Example 4 (containing 0.0031 mmol ofrhodium), 0.71 ml (6.20 mmol) of styrene, and 0.35 ml of benzene. Thecontents were stirred at 60° C. for 12 hours in an atmosphere of 10 atmcarbon monoxide and 10 atm hydrogen. A small portion of the reactionmixture was taken out and filtered to remove the catalyst. This reactionmixture was analyzed by ¹ H NMR spectrometry to determine theconversion. As a result, the conversion was found to be 99%. Theproportion of the α-methylphenylacetaldehyde to dihydrocinnamaldehydeyielded (regioselectivity) was 89:11. These reaction products wereconverted to carboxylic acids by Jones oxidation, and then analyzed byGC using a chiral column (Chrompack Cp-Cyclodex β-236M) to determine theenantiomer excess. As a result, the enantiomer excess was found to be89% ee.

EXAMPLE 6

Reuse of Catalyst

Into a 50-ml pressure bottle made of glass were introduced 63 mg of therhodium complex synthesized in Example 4 (containing 0.0031 mmol ofrhodium), 0.71 ml (6.20 mmol) of styrene, and 0.35 ml of benzene. Thecontents were stirred at 60° C. for 3 hours in an atmosphere of 2.5 atmcarbon monoxide and 2.5 atm hydrogen. As a result, the conversion was41%, the regioselectivity was 88:12, and the enantiomer excess was 86%ee. After completion of the reaction, the benzene solution supernatantcontaining the reaction products and substrate was taken out with asyringe in an argon atmosphere. After the residue was washed withbenzene, 0.71 ml (6.20 mmol) of styrene and 0.35 ml of benzene wereadded thereto to conduct a catalytic reaction in the same manner. As aresult, the conversion in this reaction was 48%, the regioselectivitywas 90:10, and the enantiomer excess was 86% ee.

EXAMPLE 7

(1) Suspension Copolymerization

To 0.4% aqueous poly(vinyl alcohol) solution was added, with sufficientstirring at 80° C., a solution prepared by dissolving 100 mg (0.122mmol) of(R)-2'-diphenylphosphino-6-vinyl-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine,0.45 ml (3.93 mmol) of styrene, 0.035 ml (0.135 mmol) of divinylbenzene,and 20.2 mg (0 .0813 mmol) of 2,2'-azobis(2,4-dimethylvaleronitrile)(hereinafter abbreviated as V-65) in 0.75 ml of toluene. The reactionmixture was stirred for 24 hours at a rotational speed of 400 rpm. Thepolymerization product obtained was taken out by filtration, washed withwater and methanol, and then dried at a reduced pressure to obtain apolymer as a light-yellow solid.

(2) Solution Copolymerization in Chloroform

Into a 20-ml Schlenk tube were introduced 100 mg (0.122 mmol) of(R)-2'-diphenylphosphino-6-vinyl-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine,0.42 ml (3.66 mmol) of styrene, 0.11 ml (0.424 mmol) of divinylbenzene,20.1 mg (0.081 mmol) of V-65, and 1.5 ml of chloroform. The contentswere heated at 70° C. for 5 hours. Methanol was added to the reactionmixture which had solidified. As a result, a white precipitategenerated. The precipitate was taken out by filtration, washed withmethanol and toluene, and then dried at a reduced pressure to obtain apolymer as a light-yellow solid.

(3) Solution Copolymerization in Toluene

Into a 20-ml Schlenk tube were introduced 100 mg (0.122 mmol) of(R)-2'-diphenylphosphino-6-vinyl-1,1'-binaphthalen-2-yloxy[(S)-6,6'-divinyl-1,1'-binaphthalene-2,2'-diyloxy]phosphine,0.42 ml (3.66 mmol) of styrene, 0.11 ml (0.424 mmol) of divinylbenzene,20.1 mg (0.081 mmol) of V-65, and 1.5 ml of toluene. The contents wereheated at 70° C. for 5 hours. Methanol was added to the reaction mixturewhich had solidified. As a result, a white precipitate generated. Theprecipitate was taken out by filtration, washed with methanol andtoluene, and then dried at a reduced pressure to obtain a polymer as alight-yellow solid.

EXAMPLE 8

Reaction of Polymer with Rhodium Dicarbonylacetylacetonate

Into a 20-ml Schlenk tube were introduced 4.1 mg (0.0159 mmol) ofRh(acac)(CO)₂, 304 mg of the polymer obtained in Example 7 (containing0.059 mmol in terms of monomer amount), and 5 ml of benzene. Thecontents were stirred with heating at room temperature for 2 hours. Thereaction mixture was freeze-dried to obtain a reaction product as ayellowish orange solid.

EXAMPLE 9

Asymmetric Hydroformylation of Styrene

Into a 50-ml stainless-steel autoclave were introduced 61 mg of therhodium complex synthesized in Example 8 (containing 0.0031 mmol ofrhodium), 0.71 ml (6.20 mmol) of styrene, and 0.35 ml of benzene. Thecontents were stirred at 60° C. for 12 hours in an atmosphere of 10 atmcarbon monoxide and 10 atm hydrogen. A small portion of the reactionmixture was taken out and filtered to remove the catalyst. This reactionmixture was analyzed by ¹ H NMR spectrometry to determine theconversion. As a result, the conversion was found to be 99%. Theproportion of the α-methylphenylacetaldehyde to dihydrocinnamaldehydeyielded (regioselectivity) was 89:11. These reaction products wereconverted to carboxylic acids by Jones oxidation, and then analyzed byGC using a chiral column (Chrompack Cp-Cyclodex β-236M) to determine theenantiomer excess. As a result, the enantiomer excess was found to be89% ee.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. A transition metal complex obtained by causing atransition metal compound to act on the polymer having structural unitsderived from a2'-diarylphosphino-1,1-biphenylen-2-yloxy(6,6'-divinyl-1,1'-binaphthalene-2,2'diyloxy)phosphinederivative which is represented by the following general formula (III)##STR15## wherein Ar is an optionally substituted phenyl group or anoptionally substituted naphthyl group; R¹ and R² each independently is ahydrogen atom, a lower alkyl group, a halogen atom, a hydrogensubstituted lower alkyl group, or a benzyloxy group; R³ is a lower alkylgroup, a lower alkoxy group, a halogen atom, a halogen substituted loweralkyl group, or a benzyloxy group; provided that R² and R³ may be bondedto each other to form a hydrocarbon ring, which may have one or moresubstituents selected from lower alkyl groups, halogen atoms, loweralkoxy groups, halogenated lower alkoxy groups, benzyloxy group, andvinyl group; and k is an integer of 2 to
 100. 2. A transition metalcomplex obtained by causing a transition metal compound to act on thepolymer having structural units ##STR16## wherein Ar is an optionallysubstituted phenyl group or an optionally substituted naphthyl group; R¹and R² each independently is a hydrogen atom, a lower alkyl group, alower alkoxy group, a halogen atom, a halogen-substituted lower alkylgroup, or a benzyloxy group; R³ is a lower alkyl group, a lower alkoxygroup, a halogen atom, a halogen-substituted lower alkyl group, or abenzyloxy group; provided that R² and R³ may be bonded to each other toform a hydrocarbon ring, which may have one or more substituentsselected from lower alkyl groups, halogen atoms, lower alkoxy groups,halogenated lower alkyl groups, a benzyloxy group, and a vinyl group; R⁴is a hydrogen atom, a lower alkyl group, a lower alkoxy group, or ahalogen atom; R⁶ is a hydrogen atom, or a methyl group; k is an integerof 2 to 100; and l and m each is an integer of 0 to 1,000; provided thatat least one of l and m is not 0 and (k+l+m) is from 10 to 1,000.
 3. Thetransition metal complex of claim 1, which has structural units derivedfrom a compound which are represented by the following general formula(VI): ##STR17## wherein Ar is an optionally substituted phenyl group oran optionally substituted naphthyl group; R¹ and R² each independentlyis a hydrogen atom, a lower alkyl group, a lower alkoxy group, a halogenatom, a halogen-substituted lower alkyl group, or a benzyloxy group; R³is a lower alkyl group, a lower alkoxy group, a halogen atom, ahalogen-substituted lower alkyl group, or a benzyloxy group; providedthat R² and R³ may be bonded to each other to form a hydrocarbon ring,which may have one or more substituents selected from lower alkylgroups, halogen atoms, lower alkoxy groups, halogenated lower alkylgroups, a benzyloxy group, and a vinyl group; M is rhodium, iridium,palladium, or platinum; W is 1,5-cyclooctadiene, norbornadiene, ahalogen atom, CO, acetoxy, allyl, or acetylacetonato; Y is a hydrogenatom, a halogen atom, ClO₄, BF₄, PF₆, BPh₄, SnCl₂, or SnCl₃ ; p and qeach is 0 to 2, provided that at least one of p and q is not 0; and k isan integer of 2 to
 100. 4. The transition metal complex of claim 2,which has structural units derived from compounds, said units beingrepresented by the following general formulae (VI), (IV), and (V):##STR18## wherein Ar is an optionally substituted phenyl group or anoptionally substituted naphthyl group; R¹ and R² each independently is ahydrogen atom, a lower alkyl group, a lower alkoxy group, a halogenatom, a halogen-substituted lower alkyl group, or a benzyloxy group; R³is a lower alkyl group, a lower alkoxy group, a halogen atom, ahalogen-substituted lower alkyl group, or a benzyloxy group; providedthat R² and R³ may be bonded to each other to form a hydrocarbon ring,which may have one or more substituents selected from lower alkylgroups, halogen atoms, lower alkoxy groups, halogenated lower alkylgroups, a benzyloxy group, and a vinyl group; R⁴ is a hydrogen atom, alower alkyl group, a lower alkoxy group, or a halogen atom; R⁶ is ahydrogen atom or a methyl group; M is rhodium, iridium, palladium, orplatinum; W is 1,5-cyclooctadiene, norbornadiene, a halogen atom, CO,acetoxy, allyl, or acetylacetonato; Y is a hydrogen atom, a halogenatom, ClO₄, BF₄, PF₆, BPh₄, SnCl₂, or SnCl₃ ; p and q each is 0 to 2,provided that at least one of p and q is not 0; k is an integer of 2 to100; and l and m each is an integer of 0 to 1,000; provided that atleast one of l and m is not 0 and (k+l+m) is from 10 to 1,000.